CN105177648A - Device for preparing semiconductor material by using pulse laser for assisting ionic liquid electrolytic deposition - Google Patents
Device for preparing semiconductor material by using pulse laser for assisting ionic liquid electrolytic deposition Download PDFInfo
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- CN105177648A CN105177648A CN201510449811.4A CN201510449811A CN105177648A CN 105177648 A CN105177648 A CN 105177648A CN 201510449811 A CN201510449811 A CN 201510449811A CN 105177648 A CN105177648 A CN 105177648A
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- laser
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- semiconductor material
- ionic liquid
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Abstract
The invention provides a method for preparing a germanium nanometer array by inducing ionic liquid electrolytic deposition through a laser and belongs to the technical field of preparing methods of a germanium nanometer array. The problems that in the existing preparing methods of the germanium nanometer array, high temperatures are required, and the preparing technology is complex and toxic are solved. The method comprises the steps that the ionic liquid electrolytic deposition technology is used for being combined with the laser irradiation technology, green ion liquid 1-ethyl-3-methylimidazole bis(trifluoromethylsulfonyl)imide which is free of toxin and pollution is used as a solvent, and Gecl4 serves as an electrolyte; and the electrolyte is irradiated by a pulse laser device, and the germanium nanometer array is prepared through one-step method electrolytic deposition. The preparing method is free of the requirement for the high temperatures, simple in technology, convenient to operate and each to achieve.
Description
Technical field
The invention belongs to semiconductor material device technical field, be specifically related to a kind of pulse laser assisting ion liquid electric that utilizes and deposit the device preparing semiconductor material.
Background technology
Electrodip process is a kind of feasible and technology of low cost in synthetic metals and alloy, has had large quantifier elimination.But because aqueous solution electrochemical window is narrower and have the precipitation of hydrogen, be difficult to deposit semiconductor material.With an organic solvent, although can obtain smooth and that homogeneity is good settling, thickness up to hundreds of nanometer, and is difficult to the impact avoiding oxidation.Numerous excellent properties that ionic liquid has, especially have unique performance in electrochemistry, as wide in electrochemical window, electric conductivity large, viscosity is relatively low, to the muriate favorable solubility etc. needed for galvanic deposit semi-conductor.Ionic liquid is easy to control as used for electrolyte in galvanic deposit semiconductor material.F.Endres team of Germany has applied ionic liquid electrodeposition method and has deposited the semiconductor materials such as Ge, Si, SiGe, Ga respectively.
Along with the progress of science and technology, more and more higher to the performance requriements of various material, sometimes single technique means cannot meet modern industry and science and technology is prepared material and the requirement of material property, therefore, in the preparation process of material, the combination of two or more preparation means being learnt from other's strong points to offset one's weaknesses is the new direction that the preparation of current material develops.Laser-assisted Electro Depositing Technology, the high-energy-density utilizing laser beam to have exactly carrys out the electrochemical reaction process in assist in electrodeposition process, thus improves sedimentation rate, improves coating performance.Laser assisted electrodeposit metals material has correlative study in aqueous, but utilizes laser assisted ionic liquid electrodeposition semiconductor material not have relevant report in addition.
Summary of the invention
The object of this invention is to provide and a kind ofly utilize pulse laser assisting ion liquid electric to deposit to prepare the device of semiconductor material, the high-energy-density that this device utilizes laser to have and with the interaction of ionic liquid to prepare semiconductor material.
The invention provides a kind of pulse laser assisting ion liquid electric that utilizes and deposit the device preparing semiconductor material, this device comprises electrochemical workstation, laser apparatus, window mirror, beam expanding lens, total reflective mirror, electrode, electrolyzer and glove box, described window mirror, beam expanding lens, total reflective mirror, electrode and electrolyzer are arranged in headgear case, window mirror, beam expanding lens and total reflective mirror set gradually on the same line from right to left, electrode and electrolyzer are arranged on the below of total reflective mirror, electrode is arranged in electrolyzer, electrode is connected with electrochemical workstation, described laser apparatus sends laser, enter in glove box through window mirror, expand after arriving beam expanding lens, the surface that laser direction is irradiated to electrolyzer is changed again through total reflective mirror.
Preferably, described electrolyzer is tetrafluoroethylene electrolyzer.
Preferably, described electrode is connected by data line with electrochemical workstation.
Beneficial effect of the present invention
The invention provides a kind of pulse laser assisting ion liquid electric that utilizes and deposit the device preparing semiconductor material, this device make use of the impact of laser on galvanic deposit system, after laser introduces electro-deposition system, interact with the electrode in system and liquid electrolyte, very large impact is brought to electrode process, first be the heat effect of laser, under the irradiation of laser, a laser photon part is absorbed by plating solution, a part incides on settling, when laser intensity not exclusively destroys settling crystalline structure, incide photon on settling will with communization electronics generation radiative collision, make photon by electron absorption.Secondly, because the action time of laser is extremely short, after the luminous energy that material absorbs changes heat energy into, heat has little time to transmit to material surface depths, then make the temperature of the surf zone of absorb photons sharply increase so that form steam, cause producing kickback pressure ripple, i.e. the power effect of laser.This device is simple, easy handling.
Accompanying drawing explanation
Fig. 1 is that the present invention utilizes pulse laser assisting ion liquid electric to deposit the device schematic diagram preparing semiconductor material;
Fig. 2 is electrolyzer of the present invention and electrochemical workstation connection diagram;
Fig. 3 is the GeCl of 0.2mol/L in embodiment 1
4at [EMIm] Tf
2cyclic voltammetry curve in N ionic liquid;
Fig. 4 is the GeCl of 0.2mol/L in embodiment 2
4with SiCl
4+ GeCl
4at [EMIm] Tf
2cyclic voltammetry curve in N ionic liquid;
The scanning electron microscope diagram sheet of the germanium of galvanic deposit when Fig. 5 is embodiment 1 energy of lasers 13mJ;
The scanning electron microscope diagram sheet of the germanium of galvanic deposit when Fig. 6 is embodiment 1 energy of lasers 23mJ;
The scanning electron microscope diagram sheet of the germanium of galvanic deposit when Fig. 7 is embodiment 1 energy of lasers 44mJ;
The scanning electron microscope diagram sheet of the germanium of galvanic deposit when Fig. 8 is embodiment 1 energy of lasers 51mJ;
The scanning electron microscope diagram sheet of the SiGe of galvanic deposit when Fig. 9 is embodiment 2 energy of lasers 23mJ;
The scanning electron microscope diagram sheet of the SiGe of galvanic deposit when Figure 10 is embodiment 2 energy of lasers 39mJ;
Figure 11 is the scanning electron microscope diagram sheet of the germanium not using laser irradiation galvanic deposit;
Figure 12 is the scanning electron microscope diagram sheet of the SiGe not using laser irradiation galvanic deposit.
Embodiment
The invention provides a kind of pulse laser assisting ion liquid electric that utilizes and deposit the device preparing semiconductor material, shown in Fig. 1, this device comprises electrochemical workstation 1, laser apparatus 2, window mirror 3, beam expanding lens 4, total reflective mirror 5, electrode 6, electrolyzer 7 and glove box 9, described window mirror 3, beam expanding lens 4, total reflective mirror 5, electrode 6 and electrolyzer 7 are arranged in headgear case 9, window mirror 3, beam expanding lens 4 and total reflective mirror 5 set gradually on the same line from right to left, electrode 6 and electrolyzer 7 are arranged on the below of total reflective mirror 5, electrode 6 is arranged on 7 li, electrolyzer, electrode 6 is connected with electrochemical workstation 1, described laser apparatus 2 sends laser, enter in glove box 9 through window mirror 3, expand after arriving beam expanding lens 4, the surface that laser direction is irradiated to electrolyzer 7 is changed again through total reflective mirror 5.Described electrode 6 (working electrode, supporting electrode, reference electrode) is connected by data line 8 with electrochemical workstation 1, electrolytic solution is injected in electrolyzer, utilize electrochemical workstation scan cycle volt-ampere (CV) curve, choose current potential and carry out constant potential galvanic deposit.
Fig. 2 is electrolyzer of the present invention and electrochemical workstation connection diagram, and wherein C represents supporting electrode, and R represents reference electrode, and W represents working electrode; Supporting electrode described in present embodiment is 99.999% platinum filament, and reference electrode is 99.999% filamentary silver, and working electrode is ITO substrate.
Electrolytic solution described in present embodiment is at the two fluoroform sulfimide salt (EMImTf of 1-ethyl-3-methylimidazole
2n) add ionogen in ionic liquid to be made into and to form, described ionogen is SiCl
4, GeCl
4or GaCl
3.Described electrolyzer is tetrafluoroethylene electrolyzer.
Below in conjunction with specific embodiment, further detailed description is done to the present invention.
Embodiment 1
1. by two for 1-ethyl-3-methylimidazole fluoroform sulfimide salt (EMImTf
2n) ionic liquid carries out secondary to it and to anhydrate process in the glove box being full of argon gas, and 100 DEG C of vacuum distilling 24h, at [EMIm] Tf
2ionogen GeCl is added in N ionic liquid
4, be made into the electrolytic solution that concentration is 0.2mol/L, after mixing, the electrolytic solution be made into needs to leave standstill 24h in glove box, and ionogen is dissolved completely in ionic liquid;
2. by ITO conductive glass substrate, use each ultrasonic cleaning 20min of acetone, methyl alcohol and ultrapure water successively, 20min is cleaned with argon plasma again after 100 DEG C of vacuum-dryings, connection electrode, using ITO substrate as working electrode, 99.999% platinum filament is as supporting electrode, and 99.999% filamentary silver, as reference electrode, utilizes tetrafluoroethylene electrolyzer 7 to limit depositional area for 0.3cm
2;
3. electrolyzer 7 is put into glove box 9, outside electrochemical workstation 1, the Princeton2273 electrochemical workstation 1 that connects connects computer, and control electrochemistry process, electrolytic solution step 1 obtained is added dropwise in electrolyzer 7, is placed in below total reflective mirror 5;
4. open pulsed laser 2, it is inner that the window mirror 3 of laser through glove box 9 back enters glove box 9, the thick 6mm of window mirror, diameter 50mm, after beam expanding lens 4 expands, arrive total reflective mirror 5 change beam direction for vertically downward, irradiate electrolyte surface, laser output wavelength 532nm, frequency adjustment is 10HZ, output voltage is adjustable as 350V respectively, 360V, 370V, 380V, 390V, 400V, 410V, 420V, 430V, 440V, 450V, 460V, 470V, 480V, 490V, the energy of corresponding arrival electrolyte surface is respectively 13mJ, 17mJ, 20mJ, 23mJ, 27mJ, 31mJ, 35mJ, 39mJ, 44mJ, 48mJ, 51mJ, 55mJ, 59mJ, 62mJ, 65mJ,
5. start Princeton2273 electrochemical workstation 1, start Powersuite software, select CyclicVoltammeter (Ramp) pattern in PowerCV to carry out cyclic voltammetric (CV) curved scanning, set that working electrode is solid state electrode, reference electrode is silver electrode and electrolyzer area 0.3cm successively
2, sweep limit-2.5V ~ 2V, scanning speed 10mV/s, starting time 15s;
6., after having scanned CV curve, select the PotentialStep pattern in PowerCorr to carry out constant potential galvanic deposit, set solid state electrode successively, reference electrode is silver electrode, electrolyzer area 0.3cm
2, deposition voltage is the recovery voltage of Ge in CV curve, depositing time 1200s, starting time 15s; After experiment terminates, close electrochemical workstation, laser apparatus, disassemble electrolyzer, preserve after ito glass substrate washes of absolute alcohol.
Fig. 3 is the GeCl of 0.2mol/L in embodiment 1
4at [EMIm] Tf
2cyclic voltammetry curve in N ionic liquid.As can be seen from Figure 3, solid black curve corresponds to the cyclic voltammetry curve not using laser irradiation, and black bands mark curve corresponds to the cyclic voltammetry curve after with 532nm laser irradiation.GeCl
4in electrolytic solution, two reduction peak in negative potential region are respectively germanic to germanous reduction peak, and germanous is to the reduction peak of germanium simple substance, and the peak in positive potential region is the oxidation peak of Ge.
Fig. 5 Fig. 6 Fig. 7 Fig. 8 be respectively embodiment 1 energy of lasers 13mJ, 23mJ, 44mJ, with 51mJ time galvanic deposit germanium, as can be seen from Fig. 5-8, cluster dress is presented with the germanium that this laser assisted electro-deposition system deposits, the shape being similar to branch is there is from 44mJ, when energy is 51mJ, dendritic shape is obvious, the length of dendroid germanium can reach 10 microns, wide 2 microns.
Figure 11 is the germanium not using laser irradiation galvanic deposit, and as can be seen from Figure 11, with comparatively large by the sample surface morphology difference of laser illumination galvanic deposit, surfacing, without obvious Cluster Phenomenon.
Embodiment 2
Identical with embodiment 1 step, difference is only that the ionogen added in step 1 is GeCl
4and SiCl
4.
Fig. 4 is the GeCl of 0.2mol/L in embodiment 2
4with SiCl
4+ GeCl
4at [EMIm] Tf
2cyclic voltammetry curve in N ionic liquid.As can be seen from the figure, SiCl
4+ GeCl
4in electrolytic solution, peak, the 3rd, negative potential region is the codeposition peak of SiGe, and the peak in positive potential region is the oxidation peak of SiGe, after laser irradiation, germanium all there occurs certain cheap with the reduction peak position peak shape of SiGe, peak area can be caused after laser radiation to increase, and proved response amount increases.Peak position obviously moves to positive potential direction, illustrates after adding laser, and reduction reaction is more easily carried out.
The SiGe of galvanic deposit when Fig. 9 and Figure 10 is respectively embodiment 2 energy of lasers 23mJ and 39mJ, as can be seen from Fig. 9 and 10, there is Cluster Phenomenon in settling, and cluster is similar to bar-shaped.Figure 12 is the SiGe not using laser irradiation galvanic deposit, and as can be seen from Figure 12, with comparatively large by the sample surface morphology difference of laser illumination galvanic deposit, surfacing, without obvious Cluster Phenomenon.
Semiconductor material prepared by the device that the present invention is a kind of to be utilized pulse laser assisting ion liquid electric to deposit to prepare semiconductor material presents different patterns under different laser energies, this device not only can be used for the material such as depositing silicon, germanium, can also be widely used in the preparation of other semiconductor material.
Claims (3)
1. one kind utilizes pulse laser assisting ion liquid electric to deposit the device preparing semiconductor material, it is characterized in that, this device comprises electrochemical workstation (1), laser apparatus (2), window mirror (3), beam expanding lens (4), total reflective mirror (5), electrode (6), electrolyzer (7) and glove box (9), described window mirror (3), beam expanding lens (4), total reflective mirror (5), electrode (6) and electrolyzer (7) are arranged in headgear case (9), window mirror (3), beam expanding lens (4) and total reflective mirror (5) set gradually on the same line from right to left, electrode (6) and electrolyzer (7) are arranged on the below of total reflective mirror (5), it is inner that electrode (6) is arranged on electrolyzer (7), electrode (6) is connected with electrochemical workstation (1), described laser apparatus (2) sends laser, enter in glove box (9) through window mirror (3), expand after arriving beam expanding lens (4), the surface that laser direction is irradiated to electrolyzer (7) is changed again through total reflective mirror (5).
2. a kind of pulse laser assisting ion liquid electric that utilizes according to claim 1 deposits the device preparing semiconductor material, and it is characterized in that, described electrolyzer (7) is tetrafluoroethylene electrolyzer.
3. a kind of pulse laser assisting ion liquid electric that utilizes according to claim 1 deposits the device preparing semiconductor material, it is characterized in that, described electrode (6) is connected by data line (8) with electrochemical workstation (1).
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|---|---|---|---|
| CN201510449811.4A CN105177648B (en) | 2015-07-28 | 2015-07-28 | A kind of utilization pulse laser assisting ion liquid electro-deposition prepares the device of semi-conducting material |
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|---|---|---|---|
| CN201510449811.4A CN105177648B (en) | 2015-07-28 | 2015-07-28 | A kind of utilization pulse laser assisting ion liquid electro-deposition prepares the device of semi-conducting material |
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| CN105177648B CN105177648B (en) | 2017-07-18 |
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Citations (6)
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|---|---|---|---|---|
| JPS60174896A (en) * | 1984-02-16 | 1985-09-09 | Mitsubishi Electric Corp | Electrolyzing device |
| CN101435110A (en) * | 2008-12-04 | 2009-05-20 | 哈尔滨工业大学 | Preparation of germanium three-dimensional photonic crystal |
| US20130112110A1 (en) * | 2011-09-21 | 2013-05-09 | Keith J. Stevenson | Chemical and electrochemical synthesis and deposition of chalcogenides from room temperature ionic liquids |
| CN103343364A (en) * | 2013-06-25 | 2013-10-09 | 哈尔滨工业大学 | Method for preparing germanium nano cubic crystals through ionic liquid electro-deposition |
| CN103606683A (en) * | 2013-11-26 | 2014-02-26 | 哈尔滨工业大学 | Coiling-type germanium nanomaterial and preparation method thereof |
| CN103741139A (en) * | 2014-01-22 | 2014-04-23 | 韶关学院 | Quick laser cladding device and cladding method of flat metal parts |
-
2015
- 2015-07-28 CN CN201510449811.4A patent/CN105177648B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60174896A (en) * | 1984-02-16 | 1985-09-09 | Mitsubishi Electric Corp | Electrolyzing device |
| CN101435110A (en) * | 2008-12-04 | 2009-05-20 | 哈尔滨工业大学 | Preparation of germanium three-dimensional photonic crystal |
| US20130112110A1 (en) * | 2011-09-21 | 2013-05-09 | Keith J. Stevenson | Chemical and electrochemical synthesis and deposition of chalcogenides from room temperature ionic liquids |
| CN103343364A (en) * | 2013-06-25 | 2013-10-09 | 哈尔滨工业大学 | Method for preparing germanium nano cubic crystals through ionic liquid electro-deposition |
| CN103606683A (en) * | 2013-11-26 | 2014-02-26 | 哈尔滨工业大学 | Coiling-type germanium nanomaterial and preparation method thereof |
| CN103741139A (en) * | 2014-01-22 | 2014-04-23 | 韶关学院 | Quick laser cladding device and cladding method of flat metal parts |
Non-Patent Citations (3)
| Title |
|---|
| ABHISHEK LAHIRI ET AL.: "UV-Assisted Electrodeposition of Germanium from an Air-and Water-Stable Ionic Liquid", 《THE JOURNAL OF PHYSICAL CHEMISTRY C》 * |
| ELI FAHRENKRUG ET AL.: "Room-Temperature Epitaxial Electrodeposition of Single-Crystalline Germanium Nanowires at the Wafer Scale from an Aqueous Solution", 《NANO LETTERS》 * |
| MINXIAN WU ET AL.: "Electrodeposition of germanium at elevated temperatures and pressures from ionic liquids", 《PHYS. CHEM. CHEM. PHYS》 * |
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